CN111808685B

CN111808685B - Detergent composition

Info

Publication number: CN111808685B
Application number: CN202010623829.2A
Authority: CN
Inventors: 李英豪; 蔡国强; 雷松亮; 屠吉利; 徐项亮; 张蕾
Original assignee: Nice Zhejiang Technology Co ltd
Current assignee: NICE ZHEJIANG TECHNOLOGY Co.,Ltd.; Nice Group Co Ltd
Priority date: 2020-06-30
Filing date: 2020-06-30
Publication date: 2021-08-24
Anticipated expiration: 2040-06-30
Also published as: CN111808685A

Abstract

The invention relates to the field of detergents, and discloses a detergent composition, which comprises the following components in part by weight: a 10-50% of surfactant, wherein C10-C14 linear alkyl benzene sulfonate accounts for at least 40% of the surfactant; b 0.1-1% of cationic polymer; the structure of the cationic polymer contains C8-C20 alkyl chains, the surface tension of a 1% deionized water solution at 25 ℃ is 35-55 mN/m, and the substitution degree of cationic groups is 0.02-0.1; c 0.2-5% of anti-redeposition polymer. According to the invention, by introducing the cationic polymer with a specific structure and adjusting the formula structure, high-content linear alkyl benzene sulfonate is kept, the anti-redeposition polymer is introduced, and the proportion of each component is further controlled, so that the negative effects of the anti-redeposition performance and detergency of the cationic polymer are eliminated while the softening effect of the washed fabric is achieved.

Description

Detergent composition

Technical Field

The invention relates to the field of detergents, in particular to a detergent composition.

Background

The detergent provides excellent stain removal effect, but after multiple washing, the detergent is affected by inorganic salt, soap scum and the like deposited on the fabric, the fabric is damaged due to friction and the like, so that the fabric is hard and the hand feeling is poor. The detergent industry has developed a variety of fabric conditioning technologies, and the most popular at present is fabric softener, which is usually added in the final rinsing stage and used in a different stage from detergent, thus increasing the operational complexity.

Cationic polymers such as cationic cellulose are commonly used as deposition aids in detergent compositions to enhance deposition of other functional materials, especially in hair-based cleaning products such as shampoos. CN105874049B discloses detergent products containing cationic cellulose based polymers. CN101151357B provides a fabric softening composition having a cationic polymer, soap and an amphoteric surfactant. CN101415809A provides a liquid laundry detergent comprising a cationic hydroxyethyl cellulose polymer, containing soap and other surfactants, which provides fabric care benefits to textiles. However, the introduction of cationic polymers presents a problem: seriously affecting the anti-redeposition effect and detergency of the detergent. In the washing process, the detergent can wash off stains on the surface of the fabric and disperse the stains in the washing solution; after the cationic polymer is combined with the cloth base, the originally negatively charged stain particles in the washing solution or washing solution can be adsorbed on the surface of the fabric, so that the fabric is dull, and the decontamination effect of the detergent is greatly reduced.

Thus, there is a need in the art for a detergent composition that avoids the negative effects of cationic polymers on anti-redeposition and soil removal while providing a softening effect by the addition of the cationic polymers.

Disclosure of Invention

In order to solve the above technical problems, the present invention provides a detergent composition. The invention ensures that the anti-redeposition capability and the detergency of the detergent are not influenced by the formula design on the basis of adding the cationic polymer into the detergent.

The specific technical scheme of the invention is as follows: a detergent composition comprising:

a. 10-50% of surfactant by weight of the total composition, wherein the C10-C14 linear alkyl benzene sulfonate accounts for at least 40% of the total weight of the surfactant;

b. cationic polymer accounting for 0.1-1% of the total weight of the composition; the structure of the cationic polymer contains C8-C20 alkyl chains, the surface tension of a 1% deionized water solution at 25 ℃ is 35-55 mN/m, and the substitution degree of cationic groups is 0.02-0.1;

c. an anti-redeposition polymer accounting for 0.2-5% of the total weight of the composition.

As discussed in the background, cationic polymers are known to impart conditioning benefits to detergents as deposition aids for benefit components. However, the introduction of the cationic polymer seriously reduces the anti-redeposition performance of the detergent composition, and is very easy to adsorb negatively charged stain particles such as carbon black, dust and the like in a washing solution onto fabrics, so that the fabrics are dull and the stain removal effect of the detergent is influenced. The present inventors have found that the selection of cationic polymers of specific structure provides both good compatibility with conventional anionic/nonionic based detergent formulations and softening benefits during the wash process. Meanwhile, the formula is strictly controlled, the higher amount of linear alkyl benzene sulfonate is kept, the anti-redeposition polymer is added, and the amounts of the anti-redeposition polymer and the cationic polymer are controlled, so that the anti-redeposition performance and the soil removal performance of the detergent composition can be greatly improved while the softening effect is obtained, and the negative effects of the anti-redeposition performance and the soil removal performance of the cationic polymer can be eliminated.

That is, the present invention can achieve the above technical effects by four aspects of (i) selecting a cationic polymer having a specific structure, + strictly limiting the linear alkyl benzene sulfonate content, + adding an anti-redeposition polymer, + controlling the ratio of the anti-redeposition polymer to the cationic polymer, and if any one of the aspects is not satisfied, the effect is greatly impaired.

In particular, the amount of the solvent to be used,

in the first aspect, the cationic polymer defined in the present invention contains C8-C20 alkyl chains, a 1% deionized water solution thereof has a surface tension of 35-55 mN/m at 25 ℃, and the degree of substitution with cationic groups of 0.02 means that the number of cationic groups contained per 100 repeating units is 2, and the degree of substitution with cationic groups of 0.1 means that the number of cationic groups contained per 100 repeating units is 10. The cationic groups may be located on the polymer backbone or on the polymer side chains. The cationic polymer with the specific structure is adsorbed to the fabric through electrostatic interaction, and the hydrophobic alkyl chain can provide a softening effect. However, if the degree of substitution of the cationic group is too high, the cationic polymer may have poor compatibility with the anionic active agent, the stability of the system may be affected, and the anti-redeposition property and detergency of the system may be excessively affected. Too low may affect its adsorption on the fabric.

In respect of the second and third aspects, it is common knowledge that the anti-redeposition performance of a detergent composition can be improved by the addition of an anti-redeposition polymer. However, the inventors have found through experimentation that the antiredeposition performance of such systems is greatly enhanced only when LAS (linear alkylbenzene sulphonate) is present in the detergent composition in an amount of greater than 40% by weight of total surfactant. If the LAS is less than 40% by weight of the total surfactant, the antiredeposition performance of the composition will remain poor even with the addition of the antiredeposition polymer. This indicates that the addition of the anti-redeposition polymer alone or the control of the high proportion of LAS in total surfactant alone does not eliminate the negative effect of the cationic polymer on the anti-redeposition effect of the detergent composition (see data in the examples section for details).

With respect to the fourth aspect, the present inventors have found through experiments that the weight ratio of the antiredeposition polymer to the cationic polymer in the detergent composition has a large influence on the antiredeposition performance of the composition. When the weight ratio of the anti-redeposition polymer to the cationic polymer is relatively low, the anti-redeposition index of the detergent composition is increased but not significant. The anti-redeposition index of the detergent composition is significantly improved when the weight ratio of anti-redeposition polymer to cationic polymer reaches a certain value (see data in the examples section for details).

Preferably, the weight ratio of the anti-redeposition polymer to the cationic polymer is 2:1 or greater.

Preferably, the cationic polymer accounts for 0.1-0.5% of the total weight of the composition; the anti-redeposition polymer accounts for 0.2-2.5% of the total weight of the composition.

Preferably, the cationic polymer is:

the modified cationic hydroxyethyl cellulose obtained by reacting hydroxyethyl cellulose with cationic etherifying agent containing alkyl long chain such as epoxypropyl dimethyl dodecyl ammonium chloride and epoxypropyl dimethyl octadecyl ammonium chloride can be further reacted with other hydrophobic etherifying agent such as glycidyl stearate and dodecyl glycidyl ether.

Or an acrylate polymer obtained by the free radical polymerization of three monomers, wherein the cationic monomer is dimethyl diallyl ammonium chloride or ethyl methacrylate trimethyl ammonium chloride, the hydrophobic monomer is lauryl acrylate or stearyl acrylate, and the hydrophilic monomer is acrylamide and hydroxyethyl methacrylate.

Preferably, the anti-redeposition polymer is selected from one or more of polyester polyether copolymer, sodium polyacrylate, polyvinylpyrrolidone, sodium carboxymethylcellulose, sodium salt of acrylic acid-maleic anhydride copolymer, polyvinyl alcohol, styrene acrylic acid copolymer, and modified polyacrylic acid.

Preferably, the anti-redeposition polymer is a polyester polyether copolymer; the polyester-polyether copolymer has a fabric-philic chain segment and a hydrophilic chain segment, wherein the fabric-philic chain segment is formed by condensation reaction of terephthalate and diol; the hydrophilic segment comprises a segment composed of repeating units of ethylene oxide.

Preferably, the diol is one or more of ethylene glycol, 1, 2-propylene glycol and 1, 3-propylene glycol.

Particularly effective polyester polyether polymers are preferably the Reel-O-Tex series of Solvay, the Texcare SRN series of Clarian.

Preferably, the pH value of the deionized water solution prepared from the detergent composition and having the mass fraction of 1% is 7-9.

The pH of the detergent composition needs to be controlled because the polyester segments in the polyester polyether copolymer are subject to hydrolysis in alkaline systems.

Preferably, the pH value of the deionized water solution prepared from the detergent composition and having the mass fraction of 1% is 7.5-8.5.

Preferably, the surfactant includes anionic surfactants other than linear alkylbenzene sulfonate, nonionic surfactants, and amphoteric surfactants.

The detergent composition further comprises one or more of a chelating agent, a washing enzyme, a fluorescent whitening agent, a perfume, a pigment, an inorganic salt, 4A zeolite, a preservative and water.

Preferably, the other anionic surfactant is one or more of fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether carboxylate, alpha-olefin sulfonate, fatty acid salt and fatty acid methyl ester sulfonate.

Preferably, the nonionic surfactant is one or more of fatty alcohol polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, alkyl glycoside, fatty acid methyl ester ethoxylate and grease ethoxylate.

Preferably, the zwitterionic surfactant may be selected from one or more of betaine type, imidazoline type and amine oxide type zwitterionic surfactants.

Further preferably, the zwitterionic surfactant is selected from one or more of cocamidopropyl betaine, lauramidopropyl amine oxide and disodium cocoamphodiacetate.

Preferably, the chelating agent is selected from one or more of Ethylenediaminetetraacetate (EDTA), methylglycine diacetate (MGDA), and glutamic acid diacetate (GLDA).

Compared with the prior art, the invention has the following technical effects: the detergent composition of the invention keeps high content of linear alkyl benzene sulfonate by introducing the cationic polymer with a specific structure and adjusting the formula structure, and simultaneously introduces the anti-redeposition polymer and further controls the proportion of each component, thereby achieving the effect of softening the washed fabric and eliminating the negative effects of the anti-redeposition performance and detergency of the cationic polymer.

Detailed Description

The present invention will be further described with reference to the following examples.

General examples

A detergent composition comprising:

Preferably, the cationic polymer is:

Preferably, the anti-redeposition polymer is a polyester polyether copolymer; the polyester polyether polymer is provided with a fabric-philic chain segment and a hydrophilic chain segment, wherein the fabric-philic chain segment is formed by condensation reaction of terephthalate and diol; the hydrophilic segment comprises a segment composed of repeating units of ethylene oxide. The diol is one or more of ethylene glycol, 1, 2-propylene glycol and 1, 3-propylene glycol. Particularly effective polyester polyether polymers may be the Reel-O-Tex series of Solvay, the TexCare SRN series of Craine.

Preferably, the pH value of a deionized water solution prepared from the detergent composition and having a mass fraction of 1% is 7-9; more preferably 7.5 to 8.5.

The surfactant includes anionic surfactants other than linear alkylbenzene sulfonate, nonionic surfactants, and amphoteric surfactants.

Preferably, the zwitterionic surfactant may be selected from one or more of betaine type, imidazoline type and amine oxide type zwitterionic surfactants. Further preferably, the zwitterionic surfactant is selected from one or more of cocamidopropyl betaine, lauramidopropyl amine oxide and disodium cocoamphodiacetate.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The starting materials and reagents used in the following examples are all common commercial products unless otherwise specified.

Trade names or abbreviations of some of the components used in the examples and comparative examples are as follows:

and (3) LAS: linear alkyl benzene sulfonic acid sodium salt, wherein the carbon atom number of the alkyl is 10-14;

AES: the fatty alcohol-polyoxyethylene ether sodium sulfate is characterized in that the carbon chain length of fatty alcohol is 12-14, and the average ethoxylation degree is 3;

AEO-9: fatty alcohol-polyoxyethylene ether, wherein the carbon chain length of the fatty alcohol is 12-14, and the average ethoxylation degree is 9;

CAB: cocamidopropyl betaine;

EDTA: ethylenediaminetetraacetic acid sodium salt;

SRN 260: a polyester polyether copolymer;

acusol 845: modified sodium polyacrylate.

The detergent compositions prepared were subjected to a softening property test according to the following method:

1. preparation of 250ppm (Ca)²⁺∶Mg²⁺3: 2) hard water, 5g of the prepared detergent composition was dissolved in 2.5L of hard water, and stirred until sufficiently dissolved;

2. putting a piece of 40 pieces of double-sided white knitted cotton cloth of 40cm multiplied by 40cm, soaking and rubbing for 30 times, then soaking for 10 minutes, rinsing for 2 times, wherein the rinsing water amount is 2L each time, wringing and drying;

3. after the above two steps were repeated 5 times, 100 other people blindly measured the softness of the white cotton cloth with hands.

The anti-redeposition performance of the detergent compositions prepared was evaluated according to the following method:

1. cutting 40 pieces of double-sided white knitted cotton cloth, polyester cotton and terylene with the size of 6cm by 6cm, wherein each piece of cloth comprises three pieces, and measuring the whiteness WI-1 of the cloth sample before washing by using Color.

2. 0.1g of carbon black powder was weighed, 2g of glycerin was added thereto and sufficiently stirred, 1L of 250ppm hard water was further added thereto and stirred for 5 minutes, 2g of a detergent was added thereto and stirred for 5 minutes.

3. 9 pieces of cloth base were put in and washed for 20 minutes (120rpm, 30 ℃) in a vertical cleaner (model RHLQ III, manufactured by national institute of chemical industry, Japan).

4. And (4) airing after washing, measuring the whiteness WI-2 after washing, and calculating the anti-redeposition index according to the following formula.

The anti-redeposition index is WI-2/WI-1 × 100, and the larger the index is, the better the anti-redeposition effect of the composition is.

The detergency effect of the prepared detergent composition was evaluated according to GBT 13174-2008 "measurement of detergency and circulating detergency for laundry detergent".

Preparation of cationic polymer 1: the method comprises the following steps of (1) hydroxyethyl cellulose and epoxypropyl dimethyl dodecyl ammonium chloride, wherein the molar ratio of repeating units of the epoxypropyl dimethyl dodecyl ammonium chloride to the hydroxyethyl cellulose is 0.03: 1, the epoxypropyl dimethyl dodecyl ammonium chloride and the hydroxyethyl cellulose are subjected to a ring-opening reaction in an isopropanol solution under the catalysis of potassium hydroxide in an inert gas environment, and the hydrophobic modified cationic hydroxyethyl cellulose is obtained after filtration, washing and drying. The degree of substitution with cationic groups was 0.03 and the surface tension of a 1% solution at 25 ℃ was 48 mN/m.

Preparation of cationic polymer 2: the hydrophobic modified cationic polymer is prepared by performing free radical polymerization on acrylamide, octadecyl acrylate and dimethyl diallyl ammonium chloride (the molar ratio of the acrylamide to the octadecyl acrylate to the dimethyl diallyl ammonium chloride is 7: 2: 1) in a tetrahydrofuran solution, and performing precipitation, filtration, washing and drying on the obtained product. The degree of substitution with cationic groups was 0.1, and the surface tension of a 1% solution at 25 ℃ was 37 mN/m.

Preparation of cationic polymer 3: the hydrophobic modified cationic hydroxyethyl cellulose is prepared by the steps of carrying out a ring opening reaction on hydroxyethyl cellulose and epoxypropyltrimethyl ammonium chloride in an isopropanol solution in an inert gas environment under the catalysis of potassium hydroxide, filtering, washing and drying, wherein the molar ratio of the repeating units of the epoxypropyltrimethyl ammonium chloride to the hydroxyethyl cellulose is 0.03: 1. The degree of substitution with cationic groups was 0.03 and the surface tension of a 1% solution at 25 ℃ was 65 mN/m.

Preparation of cationic polymer 4: acrylamide, octadecyl acrylate and dimethyl diallyl ammonium chloride (the molar ratio of the acrylamide to the octadecyl acrylate to the dimethyl diallyl ammonium chloride is 6: 2) are subjected to free radical polymerization in tetrahydrofuran solution to obtain the hydrophobic modified cationic polymer, and the hydrophobic modified cationic polymer is obtained after precipitation, filtration, washing and drying. The degree of substitution with cationic groups was 0.2 and the surface tension of a 1% solution at 25 ℃ was 41 mN/m.

Test example

The components were weighed in the amounts (wherein the contents all represent weight percent) shown in tables 1 to 4 to prepare detergent compositions. The performance of the detergent composition was evaluated, and the results are shown in tables 1 to 4.

TABLE 1 detergent compositions and anti-redeposition data thereof

Note: the "/" in all tables indicates a content of 0.

As can be seen from Table 1, the anti-redeposition index at the time of washing fabrics showed a significant drop after incorporating the cationic polymer 1 into the detergent composition (data of blank and comparative examples), indicating that the cationic polymer seriously causes stains in the washing environment to be deposited on fabrics and the cloth-like staining to be serious. The anti-redeposition performance of the detergent composition can be improved by adding an anti-redeposition polymer such as polyester polyether polymer SRN260 (the weight ratio of SRN260 to cationic polymer 1 is greater than or equal to 2: 1), but the anti-redeposition effect of the system can be greatly improved only when the LAS accounts for more than 40% of the total surfactant in the detergent composition. If the LAS makes up less than 40% by weight of total surfactant (example 1), the detergent composition will have poor anti-redeposition performance even with the addition of SRN 260. This indicates that the addition of the anti-redeposition polymer alone or the control of the high proportion of LAS in total surfactant alone does not eliminate the negative effect of the cationic polymer on the anti-redeposition effect of the detergent composition.

Table 2 detergent composition formulations and anti-redeposition data

Note: the "/" in all tables indicates a content of 0.

As can be seen from the above table, the weight ratio of anti-redeposition polymer, such as SRN260, to cationic polymer 2 in the detergent composition has a greater effect on the anti-redeposition performance of the composition. When the weight ratio of SRN260 to cationic polymer 2 was 1: 1 (example 7), the anti-redeposition index of the detergent composition increased but was not significant, and the fabric base remained heavily black. When the weight ratio of SRN260 to cationic polymer 2 is further increased to 2:1 and above, the anti-redeposition index of the detergent composition is significantly increased. The polyester polyether copolymer can be compounded with the hydrophobically modified polyacrylic acid polymer (example 8), and the anti-redeposition index of the detergent composition can be obviously improved.

Table 3 detergency and softening performance data for detergent compositions

*: calculated with the decontamination value of a standard laundry detergent of 1.00.

The soil release and softening performance of the partial detergent compositions was further evaluated. As can be seen from Table 3, the addition of cationic polymer 1 seriously affects the detergency of the detergent composition, and the detergency values of comparative examples 2 and 3 are remarkably reduced from those of the blank examples. After the anti-redeposition polymer is added, the detergency of the composition is obviously improved. Softening test results show that most of the testers believe that the detergent composition with the cationic polymer 1 can make cotton cloth softer, and the addition of the anti-redeposition polymer does not affect the softening effect of the composition.

Table 4 detergent composition formulations and softening data

As can be seen from the above table, since the cationic polymer 3 does not contain hydrophobic carbon chains, the cotton cloth does not have a softening effect after washing; therefore, the cationic polymer only contains hydrophobic carbon chains and can endow the cotton cloth with a softening effect after being adsorbed on the cotton cloth.

TABLE 5 detergent composition formulations and anti-redeposition data

From the above table, it can be seen that if the cationic group substitution degree of the cationic polymer is too large (cationic polymer 4, substitution degree of 0.2), the negative effects of the cationic polymer on anti-redeposition cannot be eliminated even if the proportion of LAS in the system to the total surfactant is high and a high proportion of anti-redeposition polymer is added. Therefore, the cationic group substitution degree of the cationic polymer is not high enough, otherwise, the anti-redeposition effect of the system cannot be improved through formula adjustment.

The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A detergent composition characterized by comprising:

c. an anti-redeposition polymer accounting for 0.2-5% of the total weight of the composition;

the weight ratio of the anti-redeposition polymer to the cationic polymer is greater than or equal to 2: 1.

2. A detergent composition according to claim 1, wherein: the cationic polymer accounts for 0.1-0.5% of the total weight of the composition; the anti-redeposition polymer accounts for 0.2-2.5% of the total weight of the composition.

3. A detergent composition according to claim 1, wherein: the cationic polymer is:

modified cationic hydroxyethyl cellulose obtained by reacting hydroxyethyl cellulose with a cationic etherifying agent containing an alkyl long chain; or the obtained modified cationic hydroxyethyl cellulose is further reacted with a hydrophobic etherifying agent to prepare a product;

4. A detergent composition according to claim 1, wherein: the anti-redeposition polymer is selected from one or more of polyester polyether copolymer, sodium polyacrylate, polyvinylpyrrolidone, sodium carboxymethyl cellulose, sodium salt of acrylic acid-maleic anhydride copolymer, polyvinyl alcohol, styrene acrylic acid copolymer and modified polyacrylic acid.

5. A detergent composition according to claim 4, wherein: the anti-redeposition polymer is a polyester polyether copolymer; the polyester-polyether copolymer has a fabric-philic chain segment and a hydrophilic chain segment, wherein the fabric-philic chain segment is formed by condensation reaction of terephthalate and diol; the hydrophilic segment comprises a segment composed of repeating units of ethylene oxide.

6. A detergent composition according to claim 1, wherein: the pH value of a deionized water solution prepared from the detergent composition and having a mass fraction of 1% is 7-9.

7. A detergent composition according to claim 6, wherein: the pH value is 7.5-8.5.

8. A detergent composition according to claim 1, wherein: the surfactant includes anionic surfactants other than linear alkylbenzene sulfonate, nonionic surfactants, and amphoteric surfactants.

9. A detergent composition according to claim 1, wherein: the detergent composition further comprises one or more of a chelating agent, a washing enzyme, a fluorescent whitening agent, a perfume, a pigment, an inorganic salt, 4A zeolite, a preservative and water.